GB2087396A - Production of chlorolactones from unsaturated carboxylic acids and novel chlorolactones so produced - Google Patents

Production of chlorolactones from unsaturated carboxylic acids and novel chlorolactones so produced Download PDF

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GB2087396A
GB2087396A GB8134276A GB8134276A GB2087396A GB 2087396 A GB2087396 A GB 2087396A GB 8134276 A GB8134276 A GB 8134276A GB 8134276 A GB8134276 A GB 8134276A GB 2087396 A GB2087396 A GB 2087396A
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acid
process according
chlorolactones
metal
carboxylic acid
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/30—Oxygen atoms, e.g. delta-lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/10—Spiro-condensed systems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Epoxy Compounds (AREA)

Description

1 GB2087396A 1
SPECIFICATION
Production of chlorolactones from unsaturated carboxylic acids and novel chlorolactones so produced This invention concerns the synthesis of chlorolactones from unsaturated carboxylic acids. The resultant chlorolactones may be used generally as intermediary synthesis products in organic chemistry or, more particularly in so far as regards rchioromethyl -y- butyrolactone or a chloromethyl 8-valerolactone, as solvents, for example for acetylene, for epoxy resins, for polyvinyl chloride and its copolymers or for other resins.
The haloactonization reaction has been known since the beginning of the twentieth century and is still of interest in synthetic organic chemistry, (see for example M.D. Dowle and D.I.
Davies, Chem. Soc. Rev., 8 (2), 171 (1979), but whereas the bromo lactones and iodolactones, which are obtained by reacting the corresponding halogen in a basic medium with an unsaturated acid according to the scheme below, have been largely described, no example is known of a direct and selective conversion of unsaturated acids to chlorolactones in an economical way; the lactonization reaction is, as a matter of fact, in competition with the dichlorination reaction as indicated in the following references:
E.E. Van Tamelen and M. Shamma, J. Am. Chem. Soc., 76, 2315 (1953); G. Berti, Gazzeta, 81, 305 (1951); G. Berti, Tetrahedron, 4, 393 (1958); W. Reppe, 0. Schlichling, K. Mager 20 and T. Toepel, Annalen, 560, 1 (1948); R. Oda, S. Muneimiya and M. Okana, J. Org. Chem., 26 (5), 1341 (1961); G.F. Bloomfield and E.H. Farmer, J. Chem. Soc., 2062 (1932); and U.S.
Patent Specification No. 4 031 115.
XCH-CH-(CH) 1 1 12 n- 25 o 1.1 c 1-1 G11 2 m 0 CH2 CH-(CH2)n7COOE + X2 base X X-CH -CE 2 1 (CH2)n-COOR In these formulae, X is a halogen atom and n is an integer, for example from 1 to 12. 35 B. Damin, J. Garapon and B. Sillion, Tetr. Letters 21, 1709 (1980), have recently described the chloroxy-carboxylation of olefines by reaction of -chloramine T- (sodium Wchloro-p-toluene sulphonamidate) in the presence of a carboxylic acid, according to the following scheme:
2--ai-cil-RI 40 E) 1 1 B-CH=CH-Rl + R11-C-011 + Ts-N-Cl,Na 0 cl O-C-R 1 I@ --< 0 0 R-CH-CH-R 1 1 1 Cl NU-To 45 where Ts is p-toluenesulphonyl (also called "tosyl"), each of R and R, which are the same or different, represents a hydrogen atoms or an aromatic or aliphatic hydrocarbon radical having from 1 to 8 carbon atoms, and R" is an aliphatic radical having from 1 to 5 carbon atoms.
However, as apparent from the reaction scheme, the chloroxycarboxylation reaction is accompa- 50 nied with the formation of a chlorotosylation product (11) in yields that may reach 15%.
The present invention is based on the surprising discovery that it is possible to form chlorolactones in high yields and without secondary chlorotosylation or dichlorination reactions.
As a general rule, the process for manufacturing chlorolactones according to the invention comprises reacting a metal N-chlorosulphonamidate with an unsaturated carboxylic acid whose 55 unsaturation is separated from the carboxylic group by at least two carbon atoms, in the presence of a strong acid whose conjugated base is a weak nucleophilic compound and preferably in an anhydrous organic solvent, the strong acid being used to displace from the metal N-chlorosulphonamiclate the corresponding acid, which constitutes the reactive element.
The unsaturated carboxylic acids that may be used in the process according to the invention 60 to produce chlorolactones, correspond more particularly to the general formulae 2 GB2087396A 2 (CH,-. CH - (C%)M COOH IL c U2/ c ROCO CH CH COOH (T2) 15 R C-, c 1 1 L3 = C---4CH2) B R3 R 1 (C112)n' -C = C ",,R2 where each of R', R 2, R3, R 4 and R5, which are the same or different, represents a hydrogen atom or an alkyl, linear or branched, radical having from 1 to 30 carbon atoms; they may be 20 also associated together to form hydrocarbon bridges; each of n, m, p, n', m' and p, which are the same or different, is 0 or an integer from 1 to 12 such that n + m + p is from 1 to 12 and n' + m' + p' is from 1 to 12.
Preferably, each of n and m is 0, 1 or 2 and p is 0 or 1, n + m + p being from 1 to 5. The same is true for n', m' and p.
Examples of unsaturated carboxylic acids that can be used in the process of the invention are: allylacetic acid (also called 4-pentenoic acid), 5hexenoic acid, 3-cyclohexene-l-carboxylic acid, (2,2,2)bicyclo-5-octene-2carboxylic acid and diallyidicarboxylic acid.
The N-chlorosulphonamidates used in the process according to the invention are more particularly those complying with the general formula:
R-Ar-S02-N-M 1 cl where R is a hydrogen atom, an alkyl radical, preferably linear, containing for example from 1 to carbon atoms, or a halogen atom, preferably chlorine; Ar is a bivalent aromatic radical containing one or more cycles, preferably a phenylene radical, whose substituents are in ortho, meta or para postion; and M is an alkali metal, preferably sodium.
As metal N-chlorosulphonamidates, there are advantageously used, according to the inven- 40 tion, products of industrial grade which as sodium Nchlorobenzenesulphonamidate (chloramine B), sodium N-chloro-p-tolulene sulphonamidate (chloramine T) and sodium N- chloro-p-chloroben zenesulphonamidate (chloramine C).
Strong acids that can be used, as a general rule, in the process of the invention are those whose dissociation in the solvent involved, results in a pKa smaller by about 2 units than the 45 pKa, determined in the same solvent, of the N-chlorosulphonamic acid corresponding to the metal N-chlorosulphonamidate involved. In practice, any acid whose pKa in water is smaller than 2.5 can be used (the pKa of N-chloro-p-toluenesulphonamic acid in water at 2WC is about 4.5). Main examples of such acids are sulphuric acid, phosphoric acid, and sulphonic acids such as aryisulphonic and alky[sulphonic acids.
In the process of the invention, the metal N-chlorosulphonamidate is generally used in a proportion of about 1 mole per mole of unsaturated carboxylic acid, and the strong acid is generally used in a proportion of 1 mole per mole of metal N- chlorosulphonamidate.
When carrying out the process according to the invention, it is important to use the N chlorosulphonamidates in an anhydrous medium and the operation will be advantageously conducted in an aromatic, aliphatic or alkylaromatic organic solvent or in a conventional halogenated solvent. Advantageously benzene or chlorobenzene is used.
In practice, the metal N-chlorosulphonamidate is suspended in the selected anhydrous organic solvent. Then, the carboxylic acid and the strong acid are simultaneously added while adjusting the flow rates of the two reactants in such a manner that the temperature of the reaction medium does not exceed 5WC. The mixture is then brought to a temperature from 50 to 13TC for a period from 0.5 to 10 hours, according to the case. After cooling, washing and filtration, the obtained chlorolactone is separated by distillation or by chromatography through a column, for example a column of silica. The chlorolactones ar4 obtained with high yields of pure products- 4 k 3 GB2087396A 3 The nature of the obtained products may be determined by different methods of analysis:
infra-red spectrography, proton magnetic nuclear resonance, carbon 13 magnetic nuclear resonance, mass spectrography and elementary analysis; these methods confirm the -chlorolac tone- structure.
The chlorolactones obtained by the above-described process are, in most cases, new products. 5 Thus, for example, 8-chloromethyl-S-valerolactone, 4-chlorocyclohexane 1- carbolactone (3) and 3-chloro cyclohexane 1-carbolactone (4), (2,2,2)bicyclo 3-chloro octane 6- carbolactone (2) and a-spiro bis (V-chloromethyi-y-butyrolactone) in the form of an equimolar mixture of the two stereoisomers.
As in the case of rchloromethyi-rbutyrolactone, these chlorolactones may be used as 10 solvents for various organic materials, particularly polymers.
On the other hand, the chlorolactonization reaction and the chlorolactones may be involved in various organic synthesis processes.
For example, advantage may be taken of the chlorolactonization reaction of unsaturated carboxylic acids, conducted as above-described, to separate two isomers whose chlorolactoniza- 15 tion velocities are different. If so desired, it will be possible to recover the carboxylic acids, which are then generally the saturated acids, by a reaction of the following type:
ci Zn -L H 20 Cuu acetic acid C 3----fClI2)3-C'OOH 0 It is also possible, from the chlorolactones, to obtain the corresponding dehalogenated lactones according to the following reaction scheme:
C1C11r 2._ U.
0 (methanol + pyridine) CH3 - 01 It is also possible to make use of the chlorolactones to obtain unsaturated lactones which are potential antitumoral agents, according to the following reaction scheme:
CICK2 ---- C DBU or DBN ",001uol 35 0 0 wherein DBU is diazo-bicyclo-undecane and DBN is diazobicyclononene.
The following examples illustrate the invention, but must not be considered in any way as 40 limiting the scope thereof.
The structure of the products obtained in each of these examples has been confirmed by elementary analysis, infrared spectrography, proton nuclear magnetic resonance, carbon 13 nuclear magnetic resonance, and mass spectrography.
-EXAMPLE 1
To a suspension of 23.9 9 (0.015 mole) of anhydrous Chloramine T in 80 mi of anhydrous benzene, there is simultaneously added, dropwise, 10. 1 g (0. 1 mole) of allylacetic acid and 10.1 9 (0.105 mole) of methanesul The reaction is very exothermic and the addition step is so controlled that the temperature 50 does not exceed WC. At the end of the addition step, the reaction mixture is brought to WC for 5 hours. After return to room temperature and filtration of the insoluble part, which is washed with some benzene, the solvent is evaporated. The -y-chloromethyl y-butyrolactone is separated by direct distillation or by passage over a silica column and elution with methyl chloride followed with distillation. BY. 1 0-2 Torr = 65-66'C. The yield of purified product is 55 63%.
-EXAMPLE 2
The operating conditions are identical to those of example 1. There is used 23.9 9 (0.105 mole) of anhydrous Chloramine T 80 mi of anhydrous chlorobenzene, 14.85 g (0.1 mole) of 5 60 hexenoic acid and 10. 1 g (0. 105 mole) of methanesulphonic acid. After 2 hours at 11 WC and a treatment similar to that of example 1, 8-chloromethyl 8-valerolactone is distilled.
B. P. 10-2 Torr = 72-73'C. The yield of purified product is 61 %.
4 GB 2 087 396A 4 -EXAMPLE 3
Identical operating conditions are used with 22.8 9 (0.1 mole) of anhydrous Chloramine T 80 mi of anhydrous chlorobenzene, 12.6 9 (0.1 mole) of 3-cyclohexene 1 -carboxylic acid and 9.6 g (0. 1 mole) of methanesulphonic acid. After one hour at WC and with a treatment identical to that described in example 1, chlorolactone is separated by distillation; two isomers are isolated: 4-chloro cyclohexane 1-carbolactone (3) and 3- chloro cyclohexane 1-carbolactone (4). The products are purified by recrystallization (melting point: 1 25'C and WC). The total yield of purified chlorolactones is 58%.
-EXAMPLE 4 The operating conditions are identical to those of the preceding examples with the use of 4.55 g (2.1 0-2 mole) of anhydrous Chloramine T 20 mi of anhydrous chlorobenzene, 3.04 g (2.1 0-2 mole) of (2,2,2)-bicyclo 5-octene 2-carboxylic acid and 19.2 g (2.10 -1 mole) of methanesulphonic acid, at WC for 3 hours. After filtration of the reaction mixture and evaporation of the solvent, the (2,2,2) bicyclo 3-chloro octane 6- carbolactone (2) is separated by 15 distillation.
B. P. 10-2 Torr = 11 WC. The yield of purified product is 77%.
1 -EXAMPLE 5
In an identical manner, 11.4 g (5.10 - 2 mole) of anhydrous Chloramine T 60 ml of anhydrous 20 chlorobenzene, 4.6 g (2.5 10-2 mole) of dially1dicarboxylic acid and 4.8 g (5.1 0-2 mole) of methanesulphonic acid are reacted at 80'C for 3 hours; after filtration and evaporation of the solvent, the a-spiro-bis-(7-chloromethyl-y-butyrolactone) is separated in a silica column by elution with methyl chloride. The product is then recrystallized (melting point 95C). The yield of purified product is 74%. The product consists of an equirnolecular mixture of the two stereoisomers.

Claims (15)

  1. CLAIMS 1. A process for manufacturing chlorolactones comprising reacting,
    in an anhydrous organic solvent and in the presence of a strong acid whose conjugated base is weakly nueleophilic, a 30 metal N-chlorosulphonamidate of the general formula:
    R-Ar-SO,-N-M 1 cl where R is a hydrogen atom, an alkyl radical or a halogen atom, Ar is a bivalent aromatic radical containing one or more rings and M is an alkali metal, with an aliphatic or alicyclic carboxylic acid having at least one ethylenic unsaturation separated from the carboxylic group by at least 40 two carbon atoms.
  2. 2. A process according to Claim 1, in which the metal Nchlorosulphonamidate is suspended in an anhydrous organic solvent and the unsaturated carboxylic acid and the strong acid are each added, in a substantially stoichiometrical proportion with respect to the metal Nchlorosulphonamidate, at a temperature lower than about WC, the resulting reaction mixture is then heated at a temperature in the range 50 to 1 WC for from 0.5 to 10 hours, and the 45 chlorolactone obtained is separated from the reaction medium and purified.
  3. 3. A process according to Claim 1 or 2, in which the carboxylic acid with ethylenic unsaturation conforms with the general formula 1 - RI-IC = C"' R-, B9,.' (C1r 2)m Ca coon CH -)- 55 IEL1 E3 23 R 2/ 60 liL- (elf) / --", COOR Horo-- 1 2 m (T2A11 50, GB2087396A 5 where each of R', R2, R 3, R 4 and R5, which are the same or different, represents a hydrogen atom or an alkyl, linear or branched, radical having from 1 to 30 carbon atoms; they may be also associated together to form hydrocarbon bridges; each of n, m, p, n', m' and p, which are the same or different, is 0 or an integer from 1 to 12 such that n + m + p is from 1 to 12 n' + m' + p' is from 1 to 12.
  4. 4. A process according to Claim 3, in which, in the formulae, each of n and m, which are the same or different, is 0, 1 or 2, p is 0 or 1, n + m + p is from 1 to 5, each of n' and m', which are the same or different, is 0,,l or 2, p' is 0 or 1, and n' + m' + p' is from 1 to 5.
  5. 5. A process according to any one of Claim 1 to 4, in which the carboxylic acid with ethylenic unsaturation is allylacetic acid, 5-hexenoic acid, 3cyclohexene-l-carboxylic acid, 10 (2,2,2)bicyclo-5-octene-2-carboxylic acid or diallyi-dicarboxylic acid.
  6. 6. A process according to any one of Claims 1 to 5, in which the metal Nchlorosulphonamidate is sodium N-chlorobenzenesulphonamidate, sodium Nchloro-p-toluenesulphonamidate or sodium N-chloro-pchlorobenzenesulphonamidate.
  7. 7. A process according to any one of Claims 1 to 6, in which the strong acid has a pKa in 15 the solvent involved 2 units lower than the pKa, in the same solvent, of the acid corresponding to the metal N-chlorosulphonamidate concerned.
  8. 8. A process according to any one of Claims 1 to 7, in which the strong acid is sulphuric acid, phosphoric acid or an aryisulphonic or alkylsulphonic acid.
  9. 9. A process according to any one of Claims 1 to 8, in which the solvent is benzene or 20 chlorobenzene.
  10. 10. A process according to Claim 1, substantially as hereinbefore described in any one of Examples 1 to 5.
  11. 11. 8-Chloromethyl-8-vaterolactone.
  12. 12. 3-Chlorocyclohexane-1 -carbolactone(4).
  13. 13. 4-Chlorocyclohexane-1 -carbolactone(3).
  14. 14. (2,2,2)bicyclo-3-chlorooctane-6-carbolactone(2).
  15. 15. a-Spiro-bis (y-chloromethyi-y-butyrolactone) in the form of an equimolecular mixture of the two stereoisomers.
    Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Ltd.-1 982. Published at The Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.
GB8134276A 1980-11-14 1981-11-13 Production of chlorolactones from unsaturated carboxylic acids and novel chlorolactones so produced Expired GB2087396B (en)

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FR8024393A FR2494271A1 (en) 1980-11-14 1980-11-14 PROCESS FOR THE PREPARATION OF CHLOROLACTONES FROM UNSATURATED CARBOXYLIC ACIDS

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US4948905A (en) * 1989-09-18 1990-08-14 Iowa State University Reasearch Foundation, Inc. Synthesis of vinyl lactones
WO2017115257A1 (en) * 2015-12-28 2017-07-06 Sabic Global Technologies B.V. Methods for producing 1-pentanols, 4-pentenoic acids, 4-pentenols, and 1-pentanoic acids

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US3870747A (en) * 1971-11-24 1975-03-11 Merck & Co Inc Intermediates and process for prostaglandin synthesis
US4010170A (en) * 1975-09-24 1977-03-01 Iowa State University Research Foundation, Inc. Butenolide synthesis via carbonylation of vinylmercurials
EP0031932B1 (en) * 1979-12-22 1987-07-01 Hüls Troisdorf Aktiengesellschaft Substituted lactones, pentanoic acid derivatives and process for their preparation

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FR2494271B1 (en) 1983-12-02
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US4413133A (en) 1983-11-01
FR2494271A1 (en) 1982-05-21
GB2087396B (en) 1984-08-30

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